EP0343362B1 - Wässrige Kadmiumoxid-Paste hoher Fliessfähigkeit für die Vibrationsfüllung von Schaum- und Faserstrukturelektrodengerüsten - Google Patents

Wässrige Kadmiumoxid-Paste hoher Fliessfähigkeit für die Vibrationsfüllung von Schaum- und Faserstrukturelektrodengerüsten Download PDF

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Publication number
EP0343362B1
EP0343362B1 EP89106572A EP89106572A EP0343362B1 EP 0343362 B1 EP0343362 B1 EP 0343362B1 EP 89106572 A EP89106572 A EP 89106572A EP 89106572 A EP89106572 A EP 89106572A EP 0343362 B1 EP0343362 B1 EP 0343362B1
Authority
EP
European Patent Office
Prior art keywords
cdo
aqueous
paste
cadmium
cadmium oxide
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
EP89106572A
Other languages
German (de)
English (en)
French (fr)
Other versions
EP0343362A2 (de
EP0343362A3 (en
Inventor
Klaus Dr. Von Benda
Gábor Dr. Benczur-Ürmössy
Gerhard Dr. Berger
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Deutsche Automobil GmbH
Original Assignee
Deutsche Automobil GmbH
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Deutsche Automobil GmbH filed Critical Deutsche Automobil GmbH
Publication of EP0343362A2 publication Critical patent/EP0343362A2/de
Publication of EP0343362A3 publication Critical patent/EP0343362A3/de
Application granted granted Critical
Publication of EP0343362B1 publication Critical patent/EP0343362B1/de
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/24—Electrodes for alkaline accumulators
    • H01M4/26—Processes of manufacture
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T29/00—Metal working
    • Y10T29/10—Battery-grid making
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T29/00—Metal working
    • Y10T29/49—Method of mechanical manufacture
    • Y10T29/49002—Electrical device making
    • Y10T29/49108—Electric battery cell making

Definitions

  • the invention relates to an aqueous cadmium oxide paste with high flowability for the vibration filling of foam and fiber structure electrode frameworks.
  • the pocket plate contains so-called briquettes, which consist of mixtures of finely divided metallic cadmium, iron oxide and graphite.
  • the finely divided cadmium is often produced by electrolytic deposition together with nickel from acidic solutions of cadmium and nickel salts.
  • the electrolytic deposition can also be carried out directly on a carrier film; the layer is then usually compacted. Electrodes with a plastic bond made of CdO or finely divided Cd on metal nets are also known.
  • Sintered framework electrodes which are preferably used for highly resilient open and gas-tight cells, contain the active Cd mass in the fine, about 10 micrometer large pores of the Sintered structure. These fine pores are impregnated by soaking them several times with a concentrated cadmium nitrate solution and precipitating cadmium hydroxide in the pores using an alkali solution. Repeated soaking and precipitation is due to the limited solubility of the cadmium salt. The process can be shortened by the electrochemical precipitation method (Kandler process) and leads to the precipitation of cadmium hydroxide and cadmium. Continuous management of the Kandler process is difficult due to the complex chemistry; it is therefore only used for the production of high quality electrodes.
  • Kandler process electrochemical precipitation method
  • foam structure and fiber structure scaffolds have been used increasingly for shaping the electrode and for holding the active mass. They consist solely of metal or they still contain the structural base made of plastic or carbon.
  • frameworks enable simple mechanical impregnation with a liquefied active compound paste.
  • the pores of the frameworks are sufficiently small to hold the mass introduced.
  • the pores are larger compared to powder metallurgy sintered frameworks, so that a suitably adjusted paste can practically penetrate completely and fill the cavities.
  • Cadmium oxide, cadmium hydroxide or cadmium powder can be used as the starting material for the paste.
  • the density of cadmium hydroxide is comparatively low at 4.8 g / cm3. This is also the achievable concentration of mass in the electrode low.
  • Cadmium hydroxide pastes are therefore not very suitable.
  • a stable paste cannot be formulated from cadmium powder alone, since the metal particles tend to settle.
  • the density of cadmium oxide is 8.15 g / cm3. This high density enables the production of cadmium electrodes with a sufficient cadmium concentration.
  • Cadmium electrodes are mainly used in nickel / cadmium cells. The necessary loading with active mass and thus the capacity is coordinated with the positive nickel electrode.
  • a modern gas-tight nickel / cadmium satellite cell with sintered electrodes (22nd IECEC, Philadelphia, August 1987, Paper 879076, Table 1) contains, for example, 12.4 g / dm2 of cadmium mass. With the specified plate thickness of 0.068 cm and 80% porosity, this corresponds to 2.28 g cadmium per cm3 empty volume. Converted to cadmium oxide, this corresponds to 2.60 g cadmium oxide / cm3. Such filling densities cannot be achieved in one operation with the cadmium oxide pastes known to date.
  • Cadmium oxide powder can be dispersed well in some selected organic liquids with a polar character. Are suitable for. B. cyclohexanol, glycolic acid butyl ester or lactic acid ethyl ester.
  • the dispersions with these organic liquids are produced, for example, in a knife mill. The loose, voluminous agglomerates of the primary cadmium oxide particles are destroyed. This is the only way to obtain liquid dispersions with up to 33% by volume of cadmium oxide (2.69 g cadmium oxide / cm3). However, these dispersions are only of limited suitability for filling foam and fiber structure structures.
  • a concentration of 21 vol.% Cadmium oxide can be achieved with water as the fluid. Over the course of a few hours, such pastes thicken as a result of the reaction of cadmium oxide and water to form cadmium hydroxide.
  • Japanese Laid-Open Patent Application (Japan Kokai Tokkyo Koho) 78 13 6634 describes an aqueous cadmium oxide paste with 14 vol.% Cadmium oxide, in which the reaction of the cadmium oxide with the water is carried out. Addition of sodium hydrogen phosphate, sodium pyrophosphate or sodium hexametaphosphate is inhibited.
  • This paste is just as unsuitable for achieving high filling densities with a single filling as the cadmium oxide paste described in DE-PS 1596023 in 30% KOH as suspension fluid.
  • cadmium oxide reacts in aqueous KOH in a few minutes in an exothermic reaction to cadmium hydroxide.
  • the object of the invention is to find an aqueous cadmium oxide paste which has such a high fluidity that the pores of foam and fiber structure electrode structures can be completely filled by it and which on the other hand has such a high cadmium oxide content that the complete filling of the porous body in one step.
  • the paste thus has a cadmium oxide content of 25 to 35% by volume, a pH of 10 to 12.5, a content of 0.5 to 2.5% by weight, based on cadmium oxide, of one or more Dispersants from the group of water-soluble salts of polyphosphoric acids, di- and polyphosphonic acids and their derivatives, gluconic acid or alkali monodimony tartrate, the paste also has a plastic viscosity of 0.1 to 1 Pa.s and a yield point between 10 and 120 Pa.
  • the cadmium oxide paste according to the invention is one of the plastic bodies.
  • An ideal plastic behavior is usually found (so-called Bingham body).
  • the viscosity is not a material constant, it can only be represented in a shear stress / velocity gradient flow diagram.
  • the paste is solid below a certain shear stress, the value corresponds to the yield point.
  • the so-called plastic viscosity is the quotient of the shear stress reduced by the yield point and the speed gradient. The yield point and the plastic viscosity describe the system completely.
  • the measurements were carried out using the Rotovisco RV 12 from Haake with the measuring devices NV and MV I. Shear speeds (speed gradients) of at least 100 / s should be achieved. The return curve was used for the evaluation. The measurements were made at 20 ° C. The paste is suitable for the vibration filling method if the flow limit is between 10 and 120 Pa and the plastic viscosity is 0.1 to 1 Pa.s.
  • the paste should preferably have a slight thixotropy (time dependence of the viscosity). After the filling process, the paste should remain liquid for a while in order to facilitate removal of excess paste from the surface of the filled body. However, it should not be so fluid that it can emerge from the pores again and form troublesome drainage drops. These conditions are reached when the yield point and viscosity are within the claimed values.
  • Dispersants from the group of water-soluble salts in particular the alkali salts of polyphosphoric acids, di and polyphosphonic acids and their derivatives, gluconic acid or also alkali metal mononyl tartrate are suitable. These dispersants are used in amounts of 0.5 to 2.5% by weight, based on cadmium oxide. According to the applicant, they act both as a dispersant and as an inhibitor of the reaction between CdO and water. The effectiveness as a dispersant and as an inhibitor increases with the chain length in the polyphosphates. Polyphosphates with 2 to 20, in particular those with 6 to 20, phosphorus atoms are therefore preferred.
  • Di- and polyphosphonic acids and their derivatives also form a particularly effective group of dispersants. Since the carbon atoms of the di- and polyphosphonic acids are degraded to carbon dioxide by the charging and discharging processes at the electrode, preference is given to using di- and polyphosphonic acids in which the ratio of C atoms to P atoms is not greater than 2 ⁇ m to keep carbonate formation in the cell as low as possible.
  • the water-soluble salts of 1-hydroxiethan-1,1-diphosphonic acid or aminotrismethylenephosphonic acid are very particularly suitable and are also commercially available inexpensively. It is known that nickel has a favorable spreading effect in small amounts in the cadmium electrode.
  • Ni x M y H z HEDP
  • M alkali metal
  • x 0.5 to 1.2
  • y 1 to 2.5
  • z 0 to 1.
  • a corresponding dispersant is produced by dissolving nickel hydroxide in the free acid H4 (HEDP) and adding alkali metal hydroxide solution.
  • suitable dispersants are the salts, in particular the alkali metal salts of gluconic acid and alkali metal mononyl tartrate. Mixtures of the dispersants can of course also be used.
  • the pH value of all pastes is shifted to higher values due to an alkalizing effect compared to the pH value of the dispersing solutions. So that the required viscosity data can be maintained, the pH must be between 10 and 12.5.
  • the paste can also contain powdery nickel hydroxide as an expanding agent in amounts of 0.25 to 3 mol%, based on cadmium.
  • Part of the active composition can also consist of cadmium powder.
  • the cadmium oxide paste then contains one part by weight of metallic cadmium powder for 1 to 15 parts by weight of cadmium oxide. This variant is particularly interesting for gas-tight nickel / cadmium cells, since they can be closed and formed immediately after assembly. The cadmium introduced then serves as a precharge reserve.
  • the paste is produced in the dispersing devices customary in the art. Knife mills and ball mills are preferred. The paste must be sheared until the required rheological characteristics are reached. Knife mills are designed to take approximately 1 to 5 minutes of exposure. The paste takes 1 to 8 hours to produce in ball mills. In the case of powdered cadmium oxide starting material, the voluminous aggregates are destroyed. If one starts from pelletized cadmium oxide, the times can be shortened, since the compression work was already done during pelleting. Pastes that comply with the claimed parameters are suitable for filling electrode structures with foam and fiber structure in one operation. The pastes are easy to process and retain their rheological and other properties over a long period of time.
  • the cadmium oxide content of the paste is 2.67 g / cm3.
  • a 0.1 molar solution of the composition Nil, 2 K1, 6 (HEDP) was used as the dispersing solution.
  • To prepare 1 l of this solution 34.33 g of 60% strength 1-hydroxyethane-1,1-diphosphonic acid (Turpinal® SL, Henkel company) were weighed into a beaker and about 800 ml of deionized water were added. 11.13 g of nickel hydroxide were dissolved therein with stirring and heating to 70 ° C. After cooling, 20 g of 47% KOH were added to this solution while stirring, causing the pH to rise to 8. The solution was made up to 1 liter.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Battery Electrode And Active Subsutance (AREA)
EP89106572A 1988-05-26 1989-04-13 Wässrige Kadmiumoxid-Paste hoher Fliessfähigkeit für die Vibrationsfüllung von Schaum- und Faserstrukturelektrodengerüsten Expired - Lifetime EP0343362B1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE3817827 1988-05-26
DE3817827A DE3817827C1 (enrdf_load_stackoverflow) 1988-05-26 1988-05-26

Publications (3)

Publication Number Publication Date
EP0343362A2 EP0343362A2 (de) 1989-11-29
EP0343362A3 EP0343362A3 (en) 1990-03-28
EP0343362B1 true EP0343362B1 (de) 1992-08-19

Family

ID=6355130

Family Applications (1)

Application Number Title Priority Date Filing Date
EP89106572A Expired - Lifetime EP0343362B1 (de) 1988-05-26 1989-04-13 Wässrige Kadmiumoxid-Paste hoher Fliessfähigkeit für die Vibrationsfüllung von Schaum- und Faserstrukturelektrodengerüsten

Country Status (5)

Country Link
US (2) US5387366A (enrdf_load_stackoverflow)
EP (1) EP0343362B1 (enrdf_load_stackoverflow)
JP (1) JPH084004B2 (enrdf_load_stackoverflow)
DE (1) DE3817827C1 (enrdf_load_stackoverflow)
ES (1) ES2045234T3 (enrdf_load_stackoverflow)

Families Citing this family (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE4015496C1 (en) * 1990-05-15 1992-01-23 Deutsche Automobilgesellschaft Mbh, 3000 Hannover, De Lead sulphate free paste of lead and lead oxide - contains up to 60 vol. per cent solids, used to impregnate support of accumulator frame
DE4015497C1 (en) * 1990-05-15 1992-01-23 Deutsche Automobilgesellschaft Mbh, 3000 Hannover, De Active aq. paste for e.g. filling grid-form lead support - contains lead, lead oxide, has plastic-fibre or -foam skeleton, used in e.g. lead accumulator, battery
ES2039158B1 (es) * 1991-12-17 1994-03-16 Acumulador Tudor S A Soc Esp D Procedimiento de preparacion de electrodos para baterias alcalinas.
US8367251B2 (en) 2007-08-30 2013-02-05 Sony Corporation Anode with lithium containing ionic polymer coat, method of manufacturing same, secondary battery, and method of manufacturing same
US8512594B2 (en) * 2008-08-25 2013-08-20 Air Products And Chemicals, Inc. Curing agent of N,N′-dimethyl-meta-xylylenediamine and multifunctional amin(s)
CN115196610B (zh) * 2022-07-19 2024-03-26 湖州英钠新能源材料有限公司 一种钠离子电池正极材料磷酸焦磷酸铁钠/碳及其合成方法和钠离子电池

Family Cites Families (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1287663B (enrdf_load_stackoverflow) * 1965-09-25 1969-01-23
GB1104432A (en) * 1965-11-24 1968-02-28 Leslie Thomas Cooper Johnson Improvements relating to devices for preventing the unauthorised movement of motor vehicles
US3890159A (en) * 1972-12-04 1975-06-17 Gen Electric Method of forming a high surface area metallic cadmium powder and an electrode therefrom
US4169075A (en) * 1974-10-10 1979-09-25 Henkel Kommanditgesellschaft Auf Aktien Process for the production of powdery washing agents by spray-drying
JPS5848990B2 (ja) * 1977-05-04 1983-11-01 三洋電機株式会社 アルカリ蓄電池用カドミウム陰極板の製法
US4608325A (en) * 1983-10-06 1986-08-26 Duracell Inc. Anode binders for electrochemical cells
US4880435A (en) * 1987-05-20 1989-11-14 Sanyo Electric Co., Ltd. Alkaline storage cell and manufacturing method therefor
DE3816232C1 (enrdf_load_stackoverflow) * 1988-05-11 1989-07-20 Deutsche Automobilgesellschaft Mbh, 3000 Hannover, De
DE3817826A1 (de) * 1988-05-26 1989-11-30 Deutsche Automobilgesellsch Waessrige nickelhydroxid-paste hoher fliessfaehigkeit
DE3822209C1 (enrdf_load_stackoverflow) * 1988-07-01 1989-11-02 Deutsche Automobilgesellschaft Mbh, 3000 Hannover, De
JP2684707B2 (ja) * 1988-09-27 1997-12-03 松下電器産業株式会社 ペースト式カドミウム負極
DE4010811C1 (enrdf_load_stackoverflow) * 1990-04-04 1991-08-08 Deutsche Automobilgesellschaft Mbh, 3000 Hannover, De

Also Published As

Publication number Publication date
JPH0224966A (ja) 1990-01-26
DE3817827C1 (enrdf_load_stackoverflow) 1989-11-09
EP0343362A2 (de) 1989-11-29
US5387366A (en) 1995-02-07
JPH084004B2 (ja) 1996-01-17
US5427158A (en) 1995-06-27
EP0343362A3 (en) 1990-03-28
ES2045234T3 (es) 1994-01-16

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